CN112920227B - Indenoindole structure-containing metallocene compound, preparation method and application thereof, and preparation method of alpha-olefin - Google Patents
Indenoindole structure-containing metallocene compound, preparation method and application thereof, and preparation method of alpha-olefin Download PDFInfo
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- CN112920227B CN112920227B CN202110189991.2A CN202110189991A CN112920227B CN 112920227 B CN112920227 B CN 112920227B CN 202110189991 A CN202110189991 A CN 202110189991A CN 112920227 B CN112920227 B CN 112920227B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 101
- 239000004711 α-olefin Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- RXXXUIOZOITBII-UHFFFAOYSA-N indeno[1,2-g]indole Chemical group C1=C2C=CC=CC2=C2C1=C1N=CC=C1C=C2 RXXXUIOZOITBII-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 239000003446 ligand Substances 0.000 claims description 34
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 24
- 239000005977 Ethylene Substances 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 230000035484 reaction time Effects 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 239000007858 starting material Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 238000006384 oligomerization reaction Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000004756 silanes Chemical class 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003426 co-catalyst Substances 0.000 claims 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 26
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 abstract description 22
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 abstract description 22
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 13
- 229940069096 dodecene Drugs 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 37
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 238000001816 cooling Methods 0.000 description 28
- 230000001681 protective effect Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 19
- 238000001914 filtration Methods 0.000 description 15
- 239000010936 titanium Substances 0.000 description 15
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 9
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- SSJXIUAHEKJCMH-PHDIDXHHSA-N (1r,2r)-cyclohexane-1,2-diamine Chemical compound N[C@@H]1CCCC[C@H]1N SSJXIUAHEKJCMH-PHDIDXHHSA-N 0.000 description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- -1 silane compound Chemical class 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical group I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention provides a metallocene compound containing an indenoindole structure, a preparation method and application thereof, and a preparation method of alpha-olefin. The indenoindole structure-containing metallocene compound has a structure shown in a formula (A) or a formula (B), can be used as a catalyst for catalyzing and synthesizing alpha-olefin, can synthesize high-carbon alpha-olefin with high activity and high selectivity, and comprises the main components of 1-octene, 1-decene and 1-dodecene.
Description
Technical Field
The invention relates to the field of organic synthesis, and particularly relates to a metallocene compound containing an indenoindole structure, a preparation method and application thereof, and a preparation method of alpha-olefin.
Background
The polyolefin product has the advantages of rich raw materials, low price, easy production and processing, good mechanical property, excellent performance and the like, so that the polyolefin product is a synthetic resin material which is most widely applied in production and life at present, and the development level of the polyolefin industry directly represents the development level of the national petrochemical industry and is an important component part in national economy and national defense strategies.
During the development of the polyolefin industry, alpha-olefins have very wide application as a distinctive terminal olefin product: olefin comonomer, emulsifier, surfactant synthetic intermediate, synthetic high-grade lubricating oil base oil and lubricating oil additive. In recent years, demand for α -olefins has rapidly increased and import has increased. Therefore, efficient production of alpha-olefins is of great importance.
At present, the production method of alpha-olefin mainly comprises ethylene oligomerization, paraffin cracking, coal gasification extraction, fatty alcohol dehydrogenation, olefin dimerization and disproportionation, internal olefin isomerization and the like; however, the selective oligomerization of ethylene to produce alpha-olefins is the most economical and potential process. For this reason, a lot of practical work has been done by the predecessors, abroad: phillips corporation in 1991 first developed a technique for the highly selective trimerization of ethylene to produce 1-hexene; then, in 2004, Sasol company takes the lead to the preparation of 1-octene by ethylene tetramerization with high selectivity; in China: in 2007, Yanshan petrochemical industry and Daqing petrochemical industry respectively realize localization of 1-hexene; patrick et al (Organometallics 2002,21, 5122-. However, the technology for preparing 1-octene and high carbon number alpha-olefin by catalyzing ethylene to oligomerize at high selectivity is still blank at home, breaks through monopoly at abroad, and makes a breakthrough in technology become a critical affair.
Disclosure of Invention
In view of the above, the present invention aims to provide a metallocene compound containing an indenoindole structure, a preparation method and an application thereof, and a preparation method of an α -olefin. The indenoindole structure-containing metallocene compound provided by the invention can be used as a catalyst for catalytic synthesis of alpha-olefin, and can be used for synthesizing alpha-olefin with high carbon number with high activity and high selectivity.
The invention provides an indenoindole structure-containing metallocene compound, which has a structure shown in a formula (A) or a formula (B):
wherein:
R 1 、R 2 、R 3 、R 4 each independently selected from: hydrogen, substituted or unsubstituted alkyl of C1-C5, substituted or unsubstituted aryl;
R 5 selected from: substituted or unsubstituted alkyl of C1-C5,Substituted or unsubstituted aryl;
R 6 、R 7 each independently selected from: substituted or unsubstituted alkyl of C1-C5, substituted or unsubstituted aryl;
x is halogen or alkyl;
m is metallic titanium, zirconium or hafnium.
Preferably, R 1 、R 2 、R 3 、R 4 Each independently selected from: hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, or tert-butyl;
R 5 selected from the group consisting of: methyl, ethyl, propyl, n-butyl or phenyl;
R 6 、R 7 each independently selected from: methyl, ethyl, phenyl or benzyl;
x is Cl or methyl;
m is Ti (III).
Preferably, the compound is selected from the formulae C1 to C14:
the invention also provides a preparation method of the metallocene compound containing the indenoindole structure in the technical scheme, which comprises the following steps:
a) reacting the starting compound with a compound n-BuLi to form an intermediate;
b) compounds of formula VI with silane Compounds (R) 5 ) 2 SiCl 2 Reacting to form a compound of formula VII;
c) reacting the intermediate obtained in the step a) with the compound of the formula VII obtained in the step b) to form a ligand;
d) the ligand is lithiated by butyl lithium and then is reacted with MCl 3 (THF) 3 Reacting to form a metallocene compound containing an indenoindole structure;
the starting compound has a structure represented by formula I or formula II:
the intermediate has a structure shown in formula III or formula IV:
the ligand has a structure represented by formula C or formula D:
the metallocene compound containing the indenoindole structure has a structure shown in a formula (A) or a formula (B):
wherein:
R 1 、R 2 、R 3 、R 4 each independently selected from: hydrogen, substituted or unsubstituted alkyl of C1-C5, substituted or unsubstituted aryl;
R 5 selected from the group consisting of: substituted or unsubstituted alkyl of C1-C5, substituted or unsubstituted aryl;
R 6 、R 7 each independently selected from: substituted or unsubstituted alkyl of C1-C5, substituted or unsubstituted aryl;
x is halogen or alkyl;
m is metallic titanium, zirconium or hafnium;
the step a) and the step b) are not limited in sequence.
Preferably, in the step a), the reaction temperature is-20-0 ℃ and the reaction time is 0.5-3 h;
in the step b):
compounds of formula VI with silane Compounds (R) 5 ) 2 SiCl 2 The reaction temperature is-78 to-10 ℃, and the reaction time is 5 to 10 hours.
Preferably, in the step c), the reaction temperature is-20 to 0 ℃, and the reaction time is 5 to 10 hours;
in the step d), the reaction temperature is-40 to 0 ℃, and the reaction time is 3 to 10 hours.
The invention also provides the application of the metallocene compound containing the indenoindole structure in the technical scheme as a catalyst for catalyzing ethylene oligomerization to synthesize alpha-olefin.
The invention also provides a preparation method of alpha-olefin, which comprises the following steps:
under the action of a catalyst, carrying out polymerization reaction on ethylene to form alpha-olefin;
the catalyst comprises a main catalyst;
the main catalyst is the metallocene compound containing the indenoindole structure in the technical scheme or the metallocene compound containing the indenoindole structure prepared by the preparation method in the technical scheme.
Preferably, the catalyst further comprises a cocatalyst;
the cocatalyst is selected from one or more of alkyl aluminoxane, a mixture of alkyl aluminum and boron-based auxiliary agent, modified alkyl aluminoxane and halogenated alkyl aluminum;
the molar ratio of the metal M in the main catalyst to the aluminum in the cocatalyst is 1: 5-5000.
Preferably, the polymerization is carried out in the presence of hydrogen;
the pressure of the ethylene is 0.1-10 MPa;
the pressure of the hydrogen is 0.1-3.0 MPa;
the reaction temperature is 25-75 ℃, and the reaction time is 5-60 min.
The indenoindole-structure-containing metallocene compound with the structure shown in the formula (A) or the formula (B) can be used as a catalyst for catalyzing and synthesizing alpha-olefin, can synthesize high-carbon-number alpha-olefin with high activity and high selectivity, and comprises the main components of 1-octene, 1-decene and 1-dodecene.
Experimental results show that the activity of the complex for catalyzing ethylene oligomerization can reach more than 176Kg/gTi (III)/h, and can reach 298.1Kg/gTi (III)/h at most; the obtained alpha-olefin products are mainly high-carbon alpha-olefins of 1-octene, 1-decene and 1-dodecene, wherein the selectivity of 1-octene is more than 23 percent and can reach as high as 30.64 percent, the selectivity of 1-decene is more than 30 percent and can reach as high as 48.71 percent, and the selectivity of 1-dodecene is more than 10 percent and can reach as high as 19.77 percent.
Detailed Description
The invention provides a metallocene compound containing an indenoindole structure, which has a structure shown in a formula (A) or a formula (B):
wherein:
R 1 、R 2 、R 3 、R 4 each independently selected from: hydrogen, substituted or unsubstituted alkyl of C1-C5, substituted or unsubstituted aryl; preferably, R 1 、R 2 、R 3 、R 4 Each independently selected from: hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
R 5 Selected from the group consisting of: substituted or unsubstituted alkyl of C1-C5, substituted or unsubstituted aryl; preferably, R 5 Selected from the group consisting of: methyl, ethyl, propyl, n-butyl or phenyl.
R 6 、R 7 Each independently selected from: substituted or unsubstituted alkyl of C1-C5, substituted or unsubstituted aryl; preferably, R 6 、R 7 Each independently selected from: methyl, ethyl, phenyl or benzyl.
X is halogen or alkyl; preferably Cl or methyl.
M is a fourth subgroup transition metal titanium, zirconium or hafnium; ti (III) is preferred.
More preferably, the indenoindole structure-containing metallocene compound is selected from the formulas C1-C14:
the indenoindole-structure-containing metallocene compound with the structure shown in the formula (A) or the formula (B) can be used as a catalyst for catalyzing and synthesizing alpha-olefin, can synthesize high-carbon-number alpha-olefin with high activity and high selectivity, and comprises the main components of 1-octene, 1-decene and 1-dodecene.
The invention also provides a preparation method of the metallocene compound containing the indenoindole structure in the technical scheme, which comprises the following steps:
a) reacting the starting compound with a compound n-BuLi to form an intermediate;
b) compounds of formula VI with silane compounds (R) 5 ) 2 SiCl 2 Reacting to form a compound of formula VII;
c) reacting the intermediate obtained in the step a) with the compound of the formula VII obtained in the step b) to form a ligand;
d) the ligand is lithiated by butyl lithium and then is reacted with MCl 3 (THF) 3 Reacting to form a metallocene compound containing an indenoindole structure;
the starting compound has a structure represented by formula I or formula II:
the intermediate has a structure shown in formula III or formula IV:
the ligand has a structure represented by formula C or formula D:
the metallocene compound containing the indenoindole structure has a structure shown in a formula (A) or a formula (B):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 The types of X and M are the same as those in the above technical solution, and are not described in detail herein.
With respect to step a): the starting compound is reacted with the compound n-BuLi to form an intermediate.
In the present invention, the starting compound has a structure represented by formula I or formula II (corresponding to the target product, formula A, formula B, respectively):
the compounds of formula I and formula II are not particularly limited in their source and may be prepared by conventional methods well known to those skilled in the art, for example, by the methods disclosed in U.S. Pat. Nos. 9657119B2, 9828403B2, 20170107307A1 and 20190085100A 1.
In the present invention, the molar ratio of the starting compound to the compound n-BuLi (i.e., n-butyllithium) is preferably 1: 1.
In the present invention, the reaction is preferably carried out under a protective atmosphere. The type of protective gas providing the protective atmosphere is not particularly limited, and may be a conventional protective gas known to those skilled in the art, such as nitrogen or argon.
In the present invention, the reaction is preferably carried out in a solvent. The solvent is preferably one or more of diethyl ether, tetrahydrofuran, methyl tert-butyl ether and diisopropyl ether. The dosage ratio of the starting compound to the solvent is preferably 1mmol to (30-100) mL.
The operation mode of the steps is particularly preferably as follows: mixing the initial compound and the solvent, cooling, then dropwise adding the n-BuLi solution, and then heating for reaction. Wherein the cooling is preferably to-10 to 0 ℃, more preferably to 0 ℃. The temperature is preferably raised to room temperature, and the temperature can be 20-25 ℃; the reaction time after the temperature rise is preferably 1.5 to 2 hours. After the reaction, an intermediate is generated in the system.
The intermediate has a structure shown in a formula III or a formula IV (corresponding to the starting compounds of the formula I and the formula II respectively):
in the structure represented by the formula III or IV, Li is bonded to any position of the corresponding aromatic ring.
With respect to step b): compounds of formula VI with silane compounds (R) 5 ) 2 SiCl 2 Reacting to form the compound shown in the formula VII.
In the present invention, the compounds of formula VI used in the subsequent ligands L4, L5 and L6 are self-synthesized, and the compounds of formula VI used in the remaining ligands are commercial products and are commercially available.
Wherein the self-synthesized compound of formula VI is prepared by: reacting a compound of formula v with dimethylamine to form a compound of formula vi:
the compound of formula V is reacted with dimethylamine ((CH) 3 ) 2 NH) is preferably 1 to (4-5).
The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of dioxane and ethylene glycol dimethyl ether. The dosage ratio of the compound shown in the formula V to the organic solvent is preferably 1mmol to (30-100) mL.
The reaction is carried out under the action of a catalyst. The catalyst is preferably copper iodide (CuI). The mol ratio of the catalyst to the compound of the formula V is preferably (0.02-0.10) to 1.
The reaction is preferably carried out in the presence of a basic substance and trans-1, 2-cyclohexanediamine. The alkaline substance is preferably a strongly alkaline substance, and more preferably anhydrous potassium hydroxide. The molar ratio of the basic substance to the compound of the formula V is preferably (1.5-2.0) to 1. The molar ratio of the compound shown in the formula V of the trans-1, 2-cyclohexanediamine is preferably (0.05-0.2) to 1. Wherein, the alkaline substance is used for removing hydrogen bromide generated by the reaction, and the trans-1, 2-cyclohexanediamine is used for in-situ coordination with the copper catalyst to generate a coordination compound.
The reaction is preferably operated in the following manner: under the protective atmosphere, firstly putting the compound of the formula V, an organic solvent, anhydrous potassium hydroxide, trans-1, 2-cyclohexanediamine and cuprous iodide into a high-pressure reaction kettle with magnetic stirring, cooling to 0 ℃, then adding frozen dimethylamine liquid into the reaction kettle, then adjusting the pressure of protective gas in the reaction kettle, and heating to a target temperature for reaction to generate the compound of the formula VI.
The kind of the protective gas providing the protective atmosphere is not particularly limited, and may be a conventional protective gas known to those skilled in the art, such as nitrogen or argon. The temperature of the frozen dimethylamine liquid is preferably-30-0 ℃. And (3) adjusting the pressure in the reaction kettle after feeding, preferably enabling the pressure of the protective gas to be 3.5-4 MPa. The target temperature is preferably 180-200 ℃, and the reaction time is preferably 10-12 h.
After the above reaction, the following post-treatments are preferably also carried out: cooling to 50-60 ℃, opening an emptying valve, continuously heating for 50-60 min to remove unreacted dimethylamine in the system as much as possible, cooling to room temperature, and filtering; mixing the obtained filtrate with dilute hydrochloric acid, adding ether for separating liquid, retaining the organic phase, continuously extracting the water phase with ether, combining the organic phases, drying with anhydrous magnesium sulfate, filtering, and removing the solvent by rotary evaporation to obtain the compound of the formula VI.
For the preparation of the compound of formula vii:
the silane compound (R) 5 ) 2 SiCl 2 In, R 5 The types of the above-mentioned components are the same as those in the above-mentioned technical solution, and are not described herein again. The silane compound (R) of the present invention 5 ) 2 SiCl 2 The source of (b) is not particularly limited, and may be a commercially available product.
The compound of formula VI and a silane compound (R) 5 ) 2 SiCl 2 The molar ratio of (b) is preferably 1: (5.0-10.0).
The reaction is preferably operated in the following manner:
s1, mixing the compound shown in the formula VI, an organic solvent and Tetramethylethylenediamine (TMEDA) under a protective atmosphere, cooling, dropwise adding n-butyllithium, and heating for reaction to obtain a reaction solution A;
s2, under a protective atmosphere, adding a silane compound (R) 5 ) 2 SiCl 2 Mixing with organic solvent, cooling, dropping the reaction liquid A, and heating to react to produce the compound of formula VI.
Regarding step S1:
the type of protective gas providing the protective atmosphere is not particularly limited, and may be a conventional protective gas known to those skilled in the art, such as nitrogen or argon. The organic solvent is preferably one or more of diethyl ether, ethylene glycol dimethyl ether and methyl tert-butyl ether. The dosage ratio of the compound shown in the formula VI to the organic solvent is preferably 1mmol to (30-100) mL. The molar ratio of the tetramethylethylenediamine to the compound shown in the formula VI is preferably (1.0-2.0) to 1. The molar ratio of n-butyllithium to the compound of formula VI is preferably 1: 1. The cooling temperature is preferably cooled to-10-0 ℃, and more preferably to 0 ℃. The temperature rise is preferably to room temperature, and can be 20-30 ℃. The reaction time is preferably 2-2.5 h.
Regarding step S2:
the type of protective gas providing the protective atmosphere is not particularly limited, and may be a conventional protective gas known to those skilled in the art, such as nitrogen or argon. The organic solvent is preferably one or more of diethyl ether, tetrahydrofuran, methyl tert-butyl ether and diisopropyl ether. The silane compound (R) 5 ) 2 SiCl 2 The dosage ratio of the organic solvent to the organic solvent is preferably 1mmol to (30-100) mL. The cooling temperature is preferably cooled to-78 to-10 ℃, more preferably to-40 ℃. The temperature rise is preferably to room temperature, and specifically can be 20-30 ℃. The reaction time is preferably 5-10 h. After reaction, the compound shown in the formula VII is generated. In the reaction process, preferably, vacuumizing is performed to remove volatile components, and after the reaction, the temperature is increased to 60-80 ℃ and vacuumizing is continuously performed for 3-5 hours; and then cooling to room temperature, adding dry diethyl ether, filtering to remove inorganic salts, and pumping out volatile components to obtain the compound shown in the formula VII.
The present invention is not particularly limited with respect to the order in which the intermediate is obtained in step a) and the compound of formula VII is obtained in step b).
With respect to step c): reacting the intermediate obtained in the step a) with the compound of the formula VII obtained in the step b) to form a ligand.
The molar ratio of the intermediate to the compound of the formula VII is preferably 1: 1. Mixing the compound shown in the formula VII with a solvent in advance, cooling, and mixing the cooled compound shown in the formula VII with the product system obtained in the step a) for reaction. The solvent is preferably one or more of diethyl ether, methyl tert-butyl ether and diisopropyl ether. The dosage ratio of the compound shown in the formula VII to the solvent is preferably 1mmol to (30-100) mL. The cooling is preferably to-50 to-30 deg.C, more preferably to-40 deg.C. Heating after the mixing, wherein the heating is preferably to room temperature, and can be 20-30 ℃; the reaction time after the temperature rise is preferably 6 to 10 hours. After the reaction, a ligand is generated.
After the above reaction, the following post-treatment is preferably further performedProcessing: concentrating the white turbid solution obtained by the reaction under vacuum condition, filtering to remove insoluble inorganic salts, draining volatile components in the filtrate, and passing the obtained crude product through CH 2 Cl 2 And recrystallizing n-hexane to obtain the ligand.
The ligand has a structure represented by formula C or formula D:
in the present invention, the synthetic route from the starting compound to the ligand is as follows:
in the present invention, the ligand is preferably selected from the group consisting of the ligands of formulae L1 to L12:
with respect to step d): the ligand is lithiated by butyl lithium and then MCl 3 (THF) 3 Reacting to form the indenoindole structure-containing metallocene compound shown in the formula (A) or the formula (B).
In the present invention, the MCl 3 (THF) 3 Preferably TiCl 3 (THF) 3 (ii) a Wherein Ti is trivalent titanium, i.e. Ti (III). In the present invention, the ligand is reacted with MCl 3 (THF) 3 Preferably 1: 1.
In the present invention, the above steps preferably specifically include:
under a protective atmosphereMixing the ligand and a solvent, cooling, dropwise adding n-butyllithium, and heating for reaction; then with previously cooled MCl 3 (THF) 3 Mixing the solutions, firstly keeping low temperature for reaction, and then heating for reaction; then, the mixture is cooled again, and methyl magnesium bromide is added dropwise to the mixture, and the mixture is heated to react, thereby producing a compound represented by the formula (A) or the formula (B).
Wherein:
the type of protective gas providing the protective atmosphere is not particularly limited, and may be a conventional protective gas known to those skilled in the art, such as nitrogen or argon. The solvent is preferably one or more of toluene, p-xylene and tetrahydrofuran. The dosage ratio of the ligand to the solvent is preferably 1mmol to (30-100) mL. The cooling is preferably to-40 to 5 ℃, and more preferably to 0 ℃. The molar ratio of n-butyllithium to ligand is preferably 1: 1. The temperature rise reaction is preferably raised to room temperature, and can be 20-30 ℃.
After the above reaction, the reaction solution obtained by the reaction was transferred to MCl which had been cooled in advance 3 (THF) 3 The solutions were mixed. The pre-cooling is preferably to a temperature of-78 to-20 deg.C, more preferably to-40 deg.C. The MCl 3 (THF) 3 The solvent in the solution is preferably one or more of toluene, p-xylene and tetrahydrofuran. Maintaining at pre-cooled MCl 3 (THF) 3 The solution is reacted at low temperature, and the reaction time is preferably 0.5-1 h. And then heating to react, wherein the heating reaction is preferably carried out for 2-3 h by firstly heating to room temperature (specifically 20-30 ℃), and then continuously heating to 60-80 ℃ for reacting for 8-10 h. After the above reaction, the following post-treatment is preferably further performed: cooling the obtained reaction solution to room temperature, filtering to remove insoluble substances, removing the solvent, and recrystallizing with toluene or n-hexane to obtain the compound represented by formula (A) or formula (B). In the invention, the catalysts C1-C12 are prepared according to the preparation process.
In the invention, if the catalysts C13-C14 are obtained, the preparation process is carried out according to the preparation process, except that after the continuous heating reaction is finished, the temperature is cooled to 0 ℃, methyl magnesium bromide is dropwise added into the mixture, and the temperature is increased for continuous reaction. The temperature rise is preferably to room temperature, and can be 20-30 ℃; the reaction time is preferably 3-4 h. After the reaction is completed, the following post-treatment is preferably performed: filtering, filtering the obtained reaction solution, evaporating the solvent in vacuum, and recrystallizing the product with toluene or n-hexane to obtain the compound shown in the formula (A) or the formula (B).
The preparation method provided by the invention is simple and feasible, has mild conditions, and can efficiently synthesize the indenoindole structure-containing metallocene compounds shown in the formulas (A) and (B).
The invention also provides application of the metallocene compound containing the indenoindole structure in the technical scheme as a catalyst for catalyzing ethylene oligomerization to synthesize alpha-olefin. The indenoindole-structure-containing metallocene compound shown in the formula (A) and/or the formula (B) can be used as a catalyst to catalyze ethylene oligomerization to synthesize alpha-olefin, can synthesize high-carbon alpha-olefin with high activity and high selectivity, and mainly comprises 1-octene, 1-decene and 1-dodecene.
The invention also provides a preparation method of alpha-olefin, which comprises the following steps:
under the action of a catalyst, ethylene is subjected to polymerization reaction to form alpha-olefin;
the catalyst comprises a main catalyst;
the main catalyst is the metallocene compound containing the indenoindole structure in the technical scheme or the metallocene compound containing the indenoindole structure prepared by the preparation method in the technical scheme.
In the present invention, the catalyst further comprises a cocatalyst. The cocatalyst is preferably one or more of alkyl aluminoxane, a mixture of alkyl aluminum and a boron-based auxiliary agent, modified alkyl aluminoxane and halogenated alkyl aluminum. Wherein, the alkyl aluminoxane is preferably one or more of methyl aluminoxane and isobutyl aluminoxane. The alkyl aluminum is preferably one or more of trimethyl aluminum, triethyl aluminum and triisobutyl aluminum. The boron-based auxiliary agent is preferably Ph 3 C[B(C 6 F 5 ) 4 ]And [ PhNH (CH) 3 ) 2 ][B(C 6 F 5 ) 4 ]One or more of them. The modified alkylaluminoxane is preferably MMAO-7 and MMAO-3A. In some embodiments of the invention, the cocatalyst is Ph 3 C[B(C 6 F 5 ) 4 ]MMAO-3A and Al (iBu) 3 。
In the invention, the molar ratio of the metal M in the main catalyst to the aluminum in the cocatalyst is preferably 1 to (5-5000), and more preferably 1 to (50-800). The molar ratio of the metal M in the main catalyst to the boron in the cocatalyst is preferably 1 to (0-2), and more preferably 1 to (0.8-2). In some embodiments of the invention, the cocatalyst is Ph 3 C[B(C 6 F 5 ) 4 ]MMAO-3A and Al (iBu) 3 Wherein, the ratio of metal Ti: b: MMAO-3A: al (iBu) 3 1: 1.2: 25: 60.
in the present invention, hydrogen is preferably introduced during the reaction. The pressure of the hydrogen is preferably 0.1 to 3.0MPa, and more preferably 0.1 to 1.0 MPa. The pressure of the ethylene raw material gas is preferably 0.1 to 10MPa, more preferably 0.1 to 5MPa, and still more preferably 0.1 to 3 MPa.
In the invention, the reaction temperature is preferably 25-75 ℃, and the reaction time is preferably 5-60 min. After the reaction, alpha-olefin is generated.
In the preparation method provided by the invention, the metallocene compound containing indenoindole structure shown in the formula (A) and/or the formula (B) is used as a main catalyst to catalyze ethylene to oligomerize and synthesize alpha-olefin, the alpha-olefin with high carbon number can be synthesized with high activity and high selectivity, and the main components of the product are 1-octene, 1-decene and 1-dodecene.
The experimental result shows that the activity of the catalyst provided by the invention can reach more than 176Kg/gTi (III)/h, and can reach 298.1Kg/gTi (III)/h at most; the obtained alpha-olefin product mainly contains several high-carbon alpha-olefins of 1-octene, 1-decene and 1-dodecene, wherein the selectivity of 1-octene is more than 23 percent and can reach as high as 30.64 percent, the selectivity of 1-decene is more than 30 percent and can reach as high as 48.71 percent, and the selectivity of 1-dodecene is more than 10 percent and can reach as high as 19.77 percent.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims. In the following examples, room temperature was 25 ℃.
EXAMPLES 1-12 preparation of ligands
S1 preparation of compound of formula vi:
under the nitrogen atmosphere, sequentially adding a compound (20mmol) of a formula V, dried dioxane (150mL), anhydrous potassium hydroxide (30mmol), trans-1, 2-cyclohexanediamine (0.2mmol) and cuprous iodide (0.15mmol) into a high-pressure reaction kettle (250mL) with magnetic stirring, cooling to 0 ℃, rapidly adding frozen dimethylamine liquid (60mmol) into the reaction kettle, adjusting the nitrogen pressure of the reaction kettle to 2.0MPa, heating to 210 ℃, and reacting for 16 hours; cooling to 80 ℃, opening an air release valve, continuously heating for 5min to evaporate unreacted dimethylamine in the system as much as possible, cooling to room temperature, filtering the reaction mixed solution, adding the filtrate into 150mL of dilute hydrochloric acid (0.1mol/L), stirring for 5min, adding ether (100mL), separating, retaining an organic phase, continuously extracting the aqueous phase with ether for three times, combining the organic phases, drying with anhydrous magnesium sulfate, filtering, and removing the solvent by rotary evaporation to obtain the compound of the formula VI.
The compounds of the formula VI used in the ligands L4, L5, L6 were synthesized by this method; the compounds of formula VI used in the remaining ligands are commercial products and are directly available commercially.
S2 preparation of the compound of formula vii:
under nitrogen atmosphere, sequentially adding a compound (20mmol) of a formula VI, tetramethylethylenediamine (TMEDA, 25mmol) subjected to molecular sieve drying treatment and dried diethyl ether (150mL) into a Schlenck bottle (250mL), cooling to 0 ℃, dropwise adding n-butyl lithium (21mmol), heating to room temperature after dropwise addition, and continuing to react for 3 hours to obtain a reaction solution A;
under a nitrogen atmosphere, in a Schlenck flask (500mL), bis (R) was added in sequence 5 ) Dichlorosilane ((R) 5 ) 2 SiCl 2 100mmol) and dry ether (150mL), cooling to-40 deg.C, adding dropwise reaction solution A, reacting for about 30min, heating to room temperature, reacting for 12h, removing volatile components under vacuum condition, and heating to room temperatureContinuously pumping for 1.5h at the temperature of 80 ℃, cooling to room temperature, adding 30mL of dry diethyl ether, filtering to remove inorganic salts, and pumping out volatile components to obtain the compound shown in the formula VII.
S3, preparing a ligand:
under nitrogen atmosphere, sequentially adding a compound (20mmol) of the formula I and dried diethyl ether (150mL) into a Schlenck bottle (250mL), cooling to 0 ℃, dropwise adding n-butyllithium (20.5mmol) into the mixture for about 30min, heating to room temperature after dropwise adding, and continuing to react for 3 h; to obtain a reaction solution containing the intermediate III.
Dripping the reaction solution into diethyl ether (50mL) solution which is cooled to-40 ℃ in advance and contains the compound (20mmol) of the formula VII, finishing dripping for about 30min, and then heating to room temperature to continue reacting for 12h to obtain a white turbid liquid system; concentrating the solution to about 30mL under vacuum, filtering to remove insoluble inorganic salts, draining the volatile components of the filtrate, passing the crude product through CH 2 Cl 2 Recrystallizing n-hexane to obtain the pure product of the ligand of the general formula (C).
By referring to the above steps, the compound of formula II is used as the starting compound to obtain the pure ligand of formula (D).
According to the preparation process, the ligands L1-L12 are respectively prepared.
Examples 13 to 26 preparation of indenoindole Structure-containing metallocene Compounds
(1) Preparation of compounds C1-C12:
dissolving 2mmol of ligand (one of L1-L12) in 30mL of toluene under nitrogen atmosphere, cooling to 0 ℃, dropwise adding 2mmol of n-butyllithium solution, removing low temperature, continuing to react for 1h at room temperature, and slowly transferring to TiCl cooled to-40 ℃ in advance by using a double-headed solvent transfer needle 3 (THF) 3 Keeping the mixture in a toluene (10mL) suspension of (2mmol, Ti is trivalent titanium, namely Ti (III)) and reacting for 0.5h at a low temperature, slowly raising the temperature to room temperature, continuing to react for 2h, raising the temperature to 60 ℃ and continuing to react for 5h, cooling to room temperature, filtering to remove insoluble substances, removing the solvent by pumping, and recrystallizing by using toluene/n-hexane to obtain the metal complex.
The metal complexes C1-C12 are obtained by respectively taking ligands L1-L12 as raw materials according to the preparation process.
(2) Preparation of compounds C13-C14:
dissolving 2mmol of ligand (one of L1-L12) in 30mL of toluene under nitrogen atmosphere, cooling to 0 ℃, dropwise adding 2mmol of n-butyllithium solution, removing low temperature, continuing to react for 1h at room temperature, and slowly transferring to TiCl cooled to-40 ℃ in advance by using a double-head solvent transfer needle 3 (THF) 3 Keeping low temperature in a toluene (10mL) suspension of (2mmol, Ti is trivalent titanium, namely Ti (III)) to react for 0.5h, slowly raising the temperature to room temperature, continuing to react for 2h, raising the temperature to 60 ℃ to continue to react for 5h, cooling to 0 ℃, dropwise adding methyl magnesium bromide (4mmol), raising the temperature to room temperature to continue to react for 1h, filtering, evaporating the solvent in vacuum, and recrystallizing the product with toluene/n-hexane to obtain the metal complex C13-C14.
Metal complexes C13 and C14 were obtained according to the above preparation procedure using ligands L1 and L11, respectively, as starting materials.
(3) Characterization and testing
The yields and mass elemental analysis test results of the products obtained in examples 13-26 are shown in Table 1:
TABLE 1 yield and elemental analysis of the products of examples 13-26
Examples 27-40 Synthesis of alpha-olefins by catalyzing ethylene
The polymerization reaction is carried out in a 500mL stainless steel high-pressure reaction kettle, the polymerization kettle with mechanical stirring is heated to 150 ℃, the vacuum pumping is carried out for 1h, the system is adjusted to the temperature condition required by the polymerization, 0.1MPa ethylene gas is filled, a methyl cyclohexane solution (the final solution total volume is 330mL) containing a certain amount of alkyl aluminum and Modified Methyl Aluminoxane (MMAO) is added into the polymerization kettle, the temperature is kept for a period of time till the temperature is constant, the stirring is started, and 0.15MPa hydrogen is introduced into the kettle till the equilibrium state is reachedIntroducing ethylene gas into the kettle to make the total pressure in the kettle reach 4.5MPa, waiting for 10min to make the ethylene reach the dissolution balance, and then adding main catalyst and Ph 3 C[B(C 6 F 5 ) 4 ]The mixed system of (1) and reacting for a period of time. Adding 10mL of ethanol into the kettle to quench the reaction, terminating the polymerization process, cooling the reaction kettle to room temperature, discharging residual kettle gas, collecting the residual kettle gas in a gas metering tank, filtering a liquid-phase product, collecting the liquid-phase product in a screw bottle, and drying an insoluble polymer obtained by filtering in a vacuum oven to obtain the mass of the insoluble polymer. And measuring the collected gas and liquid phase products and then carrying out gas chromatography analysis.
The polymerization conditions were as follows:
main catalyst: one of C1-C14, the dosage is 2.0 mu mol;
and (3) a cocatalyst: ph 3 C[B(C 6 F 5 ) 4 ]MMAO-3A and Al (iBu) 3 The proportion of the metal Ti: b: MMAO-3A: al (iBu) 3 1: 1.2: 25: 60, adding a solvent to the mixture;
the polymerization temperature is 55 ℃, the hydrogen partial pressure in the polymerization kettle is 0.15MPa, the total polymerization pressure is 4.5MPa, and the polymerization time is 30 min.
The data of the effect of the main catalyst C1-C14 on the high-selectivity oligomerization of ethylene are shown in Table 2:
table 2 shows that C1-C14 are data of ethylene high selectivity oligomerization catalyzed by main catalyst
In the above table, Kg/gTi (III)/h is the unit of activity, and the α -olefin content (%) is the mass percentage.
The experimental results show that the activity of the complex for catalyzing ethylene oligomerization can reach more than 176Kg/gTi (III)/h, and can reach 298.1Kg/gTi (III)/h at most; the obtained alpha-olefin products are mainly high-carbon alpha-olefins of 1-octene, 1-decene and 1-dodecene, wherein the selectivity of 1-octene is more than 23 percent and can reach as high as 30.64 percent, the selectivity of 1-decene is more than 30 percent and can reach as high as 48.71 percent, and the selectivity of 1-dodecene is more than 10 percent and can reach as high as 19.77 percent.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A metallocene compound containing an indenoindole structure has a structure shown in a formula (A) or a formula (B):
specifically selected from the formulas C1-C14:
2. a method for preparing a metallocene compound containing an indenoindole structure according to claim 1, comprising the steps of:
a) reacting the starting compound with a compound n-BuLi to form an intermediate;
b) compounds of formula VI with silane compounds (R) 5 ) 2 SiCl 2 Reacting to form a compound of formula VII;
c) reacting the intermediate obtained in the step a) with the compound of the formula VII obtained in the step b) to form a ligand;
d) the ligand is lithiated by butyl lithium and then is reacted with MCl 3 (THF) 3 Reacting to form a metallocene compound containing an indenoindole structure;
the starting compound has a structure represented by formula I or formula II:
the intermediate has a structure shown in a formula III or a formula IV:
the ligand has a structure represented by formula C or formula D:
the metallocene compound containing the indenoindole structure has a structure shown in a formula (A) or a formula (B):
the step a) and the step b) are not limited in sequence.
3. The preparation method according to claim 2, wherein in the step a), the reaction temperature is-20 to 0 ℃ and the reaction time is 0.5 to 3 hours;
in the step b):
compounds of formula VI with silane compounds (R) 5 ) 2 SiCl 2 The reaction temperature is-78 to-10 ℃, and the reaction time is 5 to 10 hours.
4. The preparation method according to claim 2, wherein in the step c), the reaction temperature is-20 to 0 ℃ and the reaction time is 5 to 10 hours;
in the step d), the reaction temperature is-40-0 ℃ and the reaction time is 3-10 h.
5. The use of the indenoindole structure-containing metallocene compound of claim 1 as a catalyst for the oligomerization of ethylene to alpha-olefin.
6. A method for producing an α -olefin, comprising:
under the action of a catalyst, ethylene is subjected to polymerization reaction to form alpha-olefin;
the catalyst comprises a main catalyst;
the main catalyst is the indenoindole structure-containing metallocene compound of claim 1 or the indenoindole structure-containing metallocene compound prepared by the preparation method of any one of claims 2 to 4.
7. The method of claim 6, wherein the catalyst further comprises a co-catalyst;
the cocatalyst is selected from one or more of alkyl aluminoxane, a mixture of alkyl aluminum and boron-based auxiliary agent, modified alkyl aluminoxane and halogenated alkyl aluminum;
the molar ratio of the metal M in the main catalyst to the aluminum in the cocatalyst is 1: 5-5000.
8. The production method according to claim 6, characterized in that the polymerization reaction is carried out in the presence of hydrogen;
the pressure of the ethylene is 0.1-10 MPa;
the pressure of the hydrogen is 0.1-3.0 MPa;
the reaction temperature is 25-75 ℃, and the reaction time is 5-60 min.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6818713B1 (en) * | 2003-08-11 | 2004-11-16 | Equistar Chemicals, Lp | Process for making polyethylene |
| CN1681848A (en) * | 2002-08-02 | 2005-10-12 | 伊奎斯塔化学有限公司 | Process for making low-density polyolefins |
| CN1756776A (en) * | 2003-03-05 | 2006-04-05 | 伊奎斯塔化学有限公司 | Propylene polymerization process |
| CN1809596A (en) * | 2003-06-20 | 2006-07-26 | 伊奎斯塔化学有限公司 | Multi-catalyst system for olefin polymerization |
| CN1849346A (en) * | 2003-09-09 | 2006-10-18 | 伊奎斯塔化学有限公司 | Hydrosilane additives for increased polyolefin molecular weight |
| CN106543302A (en) * | 2015-09-18 | 2017-03-29 | 中国石油天然气股份有限公司 | Double-core heterocyclic catalyst and its application in propylene homo and copolymerization |
| CN108250252A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | Bridged combined metal compound containing heterocycle structure and its preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6982305B2 (en) * | 2004-01-26 | 2006-01-03 | Equistar Chemicals, Lp | Olefin polymerization in the presence of a dehydrogenation catalyst |
| US7638586B2 (en) * | 2006-09-26 | 2009-12-29 | Equistar Chemicals, Lp | Olefin polymerization process |
-
2021
- 2021-02-18 CN CN202110189991.2A patent/CN112920227B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1681848A (en) * | 2002-08-02 | 2005-10-12 | 伊奎斯塔化学有限公司 | Process for making low-density polyolefins |
| CN1756776A (en) * | 2003-03-05 | 2006-04-05 | 伊奎斯塔化学有限公司 | Propylene polymerization process |
| CN1809596A (en) * | 2003-06-20 | 2006-07-26 | 伊奎斯塔化学有限公司 | Multi-catalyst system for olefin polymerization |
| US6818713B1 (en) * | 2003-08-11 | 2004-11-16 | Equistar Chemicals, Lp | Process for making polyethylene |
| CN1849346A (en) * | 2003-09-09 | 2006-10-18 | 伊奎斯塔化学有限公司 | Hydrosilane additives for increased polyolefin molecular weight |
| CN106543302A (en) * | 2015-09-18 | 2017-03-29 | 中国石油天然气股份有限公司 | Double-core heterocyclic catalyst and its application in propylene homo and copolymerization |
| CN108250252A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | Bridged combined metal compound containing heterocycle structure and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| "Heterocycle-Fused Indenyl Silyl Amido Dimethyl Titanium Complexes as Catalysts for High Molecular Weight Syndiotactic Amorphous Polypropylene";Grandini, Cristiano等;《Organometallics》;20041231;第23卷(第3期);344-360 * |
| "茂金属催化体系下煤制α－烯烃制备低黏度ＰＡＯ基础油的工艺研究";马跃锋等;《石油炼制与化工》;20160630;第47卷(第6期);32-36 * |
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